CN101113486A - Melted iron desulfuration pretreatment furnace slag modifier and method for making same - Google Patents
Melted iron desulfuration pretreatment furnace slag modifier and method for making same Download PDFInfo
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- CN101113486A CN101113486A CNA2007100924118A CN200710092411A CN101113486A CN 101113486 A CN101113486 A CN 101113486A CN A2007100924118 A CNA2007100924118 A CN A2007100924118A CN 200710092411 A CN200710092411 A CN 200710092411A CN 101113486 A CN101113486 A CN 101113486A
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- desulfurization
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Abstract
The invention discloses a molten iron desulfurization pretreatment slag modifier and a preparation method thereof. The molten iron desulfurization pretreatment slag modifier takes glass powder, potassium feldspar, fluorite and soda as raw materials and is made by the refining processes of crashing, compounding and granulating through a disc-typed granulator, etc. According to the weight proportion, the chemical components of the modifier are 49-57 percent of SiO2, 18-25 percent of CaF2, 2-5 percent of Al2O3, 2-6 percent of CaO and 15-25 percent of K2O and Na2O. The molten iron desulfurization pretreatment slag modifier of the invention is suitable for being used in the molten iron desulfurization pretreatment technology by adopting CaO-Mg as desulfurization agent. The desulfurization slag modifier is of good capabilities in lowering slag basicity and slag melting temperature and improving rheology character and aggregation performance of desulfurization slag. By improving slag surface tension and lowering slag viscosity, the invention realizes the purposes of reducing slag iron content, slag skimming time and temperature drop and improving production efficiency.
Description
Technical field
The present invention relates to melted iron desulfuration pretreatment furnace slag modifier, particularly a kind of the CaO-Mg sweetening agent is carried out the properties-correcting agent of slag behind the desulfurizing iron, belong to the hot metal pretreatment field.
Technical background
Hot metal pretreatment is that molten steel sulfur content is controlled in the reasonable range, to shorten the converter smelting time, improves the converter working efficiency, reduces steel-making cost.Yet big, the difficult problem of skimming of the band iron amount of skimming after the desulfurization of desulfurizing iron pre-treatment ubiquity is in the CaO-Mg sulfur removal technology of particularly jetting, because the iron loss that band iron causes in the slag reaches about 5Kg/t iron.From production practice, there are problems such as basicity height, mobile difference in the slag after the desulfurization, causes slag-removing time long, and a large amount of molten iron run off along with slag in the process of skimming, and the molten iron loss is serious, directly has influence on output and iron and steel stock consumption indicators.
The clear 55-47310 of Japanese Patent " the easy flux of foundry ladle slag blanket " discloses a kind of desulfurization slag solidified modification agent that prevents, its chemical ingredients (weight %) is: SiO
250～70%, Al
2O
320～36%, Na
2O+K
2O 10～15%.Before average desulfurization under the situation of jar the slag amount of bringing into iron 1.67Kg per ton approximately, doctor solution consumption iron 1.23Kg per ton approximately, add-on with iron 0.4Kg per ton approximately adds modification agent in the desulfurization container before desulfurization, by reacting the flowability that generates the low melting point slag and improve slag by the thermit reaction additional heat with the desulfurization slag, make that to take off slag operation smooth, the molten iron recovery rate improves.The subject matter of its existence: 1. upgrading is limited in one's ability.When calcium oxide content is higher in the slag after before the desulfurization jar of slag amount of bringing into is than big and desulfurization, with SiO
2And Al
2O
3For the modification agent of main component reduces slag melting, the ability of improving the flowability of slag just seems not enough.2. the Al in this modification agent
2O
3After adding the reaction of aluminium powder and ferric oxide, obtain.Aluminium powder costs an arm and a leg, modification agent cost height.China Patent No. 98100567.5 discloses a kind of desulfurizing slag modifier, and its chemical ingredients (weight %) is: Na
2CO
335～50%, SiO
235～50%, CaF
28～15%, surplus is Fe
2O
3, P
2O
5With other unavoidable impurities.This properties-correcting agent is applicable to CaO to be that the desulfurization slag of main component carries out modification, has certain modified effect.But be not suitable for the modification of slag after slag amount is bigger before CaO-Mg desulfurization and the desulfurization the desulfurization.
For the modification with slag after the desulfurization that slag amount is bigger before CaO-Mg desulfurization and the desulfurization is the key problem in technology of optimizing desulfurizing iron technology, also is purpose of the present invention.
Summary of the invention
At the prior art above shortcomings, the object of the present invention is to provide and a kind ofly can effectively reduce temperature of fusion and the viscosity that the CaO-Mg sweetening agent is handled desulfurization slag behind the molten iron, significantly improve CaO-Mg desulfurization slag rheological characteristics and assemble the melted iron desulfuration pretreatment furnace slag modifier of performance.
Another object of the present invention provides the described melted iron desulfuration pretreatment furnace slag modifier method of preparation.
Purpose of the present invention realizes in the following manner: this CaO-Mg melted iron desulfuration pretreatment furnace slag modifier is formed by glass powder, potassium felspar sand, fluorite and soda formulated; The chemical ingredients of this melted iron desulfuration pretreatment furnace slag modifier (weight %) satisfies: SiO
249～57%, CaF
218～25%, Al
2O
32～5%, CaO 2～6% and K
2O+Na
2O 15～25%.
For guaranteeing that this properties-correcting agent has the good rheological characteristics of improving the desulfurization slag and assembles performance, wherein the chemical constitution of raw material (weight %) satisfies respectively:
Glass powder: SiO
269～72%, CaO 10～11%, Na
2O 10～15%, 0＜Al
2O
3＜2.0%, 0＜S＜0.03%, 0＜MgO＜0.86%, 0＜Fe
2O
3＜0.9%;
Potassium felspar sand: SiO
274～80%, Al
2O
310～14%, K
2O+Na
2O 8～10%;
Fluorite: CaF
285～90%, 0＜SiO
2＜5.0%, 0＜S＜0.05%;
Soda: Na
2CO
3＞95% (at high temperature is decomposed into Na
2O+CO
2).
The preparation method of the melted iron desulfuration pretreatment furnace slag modifier that the present invention relates to comprises following steps:
1) chemical ingredients of detection starting material glass powder, potassium felspar sand, fluorite and soda;
2) chemical ingredients (weight %) according to melted iron desulfuration pretreatment furnace slag modifier is: SiO
249～57%, CaF
218～25%, Al
2O
32～5%, CaO 2～6% and K
2O+Na
2O 15～25%, calculate required raw-material weight;
3) the above-mentioned starting material that take by weighing are in proportion melted evenly the back naturally cooling of coming out of the stove in the hot stove in ore deposit;
4) the above-mentioned raw materials fragmentation is worked into 200 orders;
5) in pan-type pelletizer, add broken good starting material, all mixed 5 minutes by prescription; The normal-temperature water that adds 1.0～1.5% (weight) more at a slow speed, the granulation material is discharged in granulation 8～15 minutes.
6) send the granulation material to the drying bed inner drying, product requirement moisture content is less than 0.5%, and granularity packs stand-by less than 3-5mm.
From chemical analysis as can be known, with SiO
2, CaF
2And Na
2O is the properties-correcting agent energy of main component and to generate fusing point with the slag congruent melting after the desulfurization of CaO-Mg sweetening agent low, the slag that rheological characteristics is good.SiO
2Be used on the one hand reducing the fusing point of slag after the desulfurization; On the other hand, be used for assembling the slag after the desulfurization of CaO-Mg sweetening agent, be easy to remove.Therefore, SiO
2Content should account for quite a few.CaF
2Be widely used as fusing assistant in metallurgy industry, it can make fusing point significantly reduce.CaF
2The adding of fusing assistant can both reduce the viscosity of slag to a certain extent, and slag absorbs and the dynamic conditions of fusion oxide compound thereby improve.F
-The fusion of CaO can be promoted, O can be replaced again
2-, impel the silica ion to disintegrate, division forms less composite anion, thereby slag viscosity is reduced.Al
2O
3As intermediate oxide, its influence is from two aspect effects.Though it and SiO
2Equally be " network " organizer, but its effect is than SiO
2A little less than, its increase has just reduced SiO relatively
2Effect, make slag " network " degree weaken, viscosity decreases; On the other hand, because Al
2O
3Can form low-melting compound with other oxide compounds, reduce the temperature of fusion of CaO-Mg desulfurization slag, improve the rheological characteristics of slag and assembled performance.Na in the properties-correcting agent
2O is provided by glass powder, potassium felspar sand and soda, Na
2O has certain sweetening power and reduces the temperature of fusion of desulfurization slag.Simultaneously, Na
2O and K
2O had both reduced the fusing point of desulfurization slag as typical basic oxide, can destroy " network " structure of composite anion again, thereby reduced viscosity coefficient of dross.
It is big to the present invention is directed to the iron loss that CaO-Mg base desulfurizer hot metal pretreatment exists, slag iron separation difficulty, and slag-removing time is long, the problem that temperature losses of the process is big and proposing, use the present invention has following characteristics:
Even 1, under the situation of this properties-correcting agent slag before containing a large amount of desulfurization, also have fine reduction basicity of slag, reduce the slag temperature of fusion and can improve the rheological characteristics of scum after the desulfurization and assemble performance; Thereby by improving the slag interfacial characteristics, reduce CaO-Mg desulfurization slag viscosity, fundamentally reduce band iron amount in the slag, reduce the iron loss in the preprocessing process, make and take off slag operation and more easily carry out, reduce slag-removing time, reduce the preprocessing process temperature drop, help improving logistics, the control rhythm of production.
2, this properties-correcting agent itself has certain sweetening power, when especially being suitable for the CaO-Mg desulfurization, and the big needs of slag amount fluctuation before the desulfurization in the iron flask; And the consumption of properties-correcting agent is few, and modified effect is good.
3, this properties-correcting agent cost of material is low, the source is wide, cost is low.
Embodiment
Below in conjunction with concrete example the present invention is done to describe in detail.
Embodiment 1:
Melted iron desulfuration pretreatment furnace slag modifier is formed by glass powder, potassium felspar sand, fluorite and soda formulated; Its chemical ingredients (weight %) satisfies: SiO
250%, CaF
219%, Al
2O
33%, CaO 3% and K
2O+Na
2O 24%.
For realize that properties-correcting agent melts evenly on melted iron desulfuration pretreatment furnace slag, give full play to the various functions of desulfurizing furnace dreg modifying agent, properties-correcting agent of the present invention adopts following technique process preparation: at first, detect the chemical ingredients of starting material glass powder, potassium felspar sand, fluorite and soda; Secondly, according to above-mentioned chemical ingredients, calculate required raw-material weight; Again the above-mentioned starting material that take by weighing are in proportion melted evenly the back naturally cooling of coming out of the stove in the hot stove in ore deposit; Fragmentation is worked into 200 orders; In pan-type pelletizer, add broken good starting material, all mixed 5 minutes by prescription; The normal-temperature water that adds 1.0～1.5% (weight) more at a slow speed, the granulation material is discharged in granulation 8～15 minutes.Send the granulation material to the drying bed inner drying, product requirement moisture content is less than 0.5%, and granularity is less than 3-5mm, and the sealing pack is stand-by.
The condition of molten iron sees Table 1, and its Intake Quantity is 77～83 tons (on average), and the slag amount of bringing into is about under the situation of 1.3 tons (on average) before the desulfurization, and the different iron melt desulfurizing agent of jetting before the desulfurizing iron, adds the furnace slag modifier of 60Kg in iron ladle on the winding-up platform.
The condition wt% of table 1 molten iron
| C | Si | Mn | P | S | V | Ti | As | Temperature, ℃ |
| 4.3～ 4.6 | 0.335～ 0.520 | 0.230～ 0.654 | 0.105～ 0.112 | 0.020～ 0.070 | 0.040～ 0.050 | 0.120～ 0.240 | 0.005～ 0.007 | 1250～ 1370 |
The modified effect of its different sweetening agent winding-up back desulfurization slags sees Table 2:
Take off the modified effect of back slag during the different sweetening agent of table 2
| The sweetening agent prescription, wt | 10％Mg+90％CaO | 20％Mg+80％CaO | 15％Mg+80％CaO+5％CaF 2 |
| The properties-correcting agent consumption, Kg | 60 | 60 | 60 |
| Slag-removing time, min | 9.5 | 8.4 | 6.5 |
| TFe，％ | 25 | 30 | 18 |
In the table 2, under the identical condition of other condition, to analyze the modified effect of melted iron desulfuration pretreatment furnace slag modifier by the prescription that changes sweetening agent.When sweetening agent is 15%Mg+80%CaO+5%CaF
2The time, band iron amount is minimum in its slag-removing time and the slag, illustrates that this properties-correcting agent has improved the rheological characteristics of slag and assembled performance, its modified effect is best.
Embodiment 2:
Melted iron desulfuration pretreatment furnace slag modifier chemical ingredients (weight %) be: SiO
252%, CaF
218%, Al
2O
34%, CaO 4% and K
2O+Na
2O 21%.Its preparation method is with embodiment 1.
The iron ladle band quantity of slag before hot metal composition and weight, the desulfurization in the iron ladle, adding mode are all identical with embodiment 1 with add-on.
The modified effect of its different sweetening agent winding-up back desulfurization slags sees Table 3:
Table 3 properties-correcting agent takes off the modified effect of back slag to using different sweetening agents
| The sweetening agent prescription, wt | 10％Mg+90％CaO | 20％Mg+80％CaO | 15％Mg+80％CaO+5％CaF 2 |
| The properties-correcting agent consumption, Kg | 60 | 60 | 60 |
| Slag-removing time, min | 9.2 | 8.0 | 6.8 |
| TFe，％ | 24 | 33 | 16 |
In the table 3, on the basis of embodiment 1, change the prescription of melted iron desulfuration pretreatment furnace slag modifier, properties-correcting agent to different sweetening agent desulfurization after the modified effect of slag identical with table 2 trend.
Embodiment 3:
The chemical ingredients of melted iron desulfuration pretreatment furnace slag modifier is formed as embodiment 1, and the present embodiment sweetening agent is identical, and its prescription all is 15%Mg+80%CaO+5%CaF
2The consumption difference of the melted iron desulfuration pretreatment furnace slag modifier that adds in every stove iron ladle, other conditions are identical with embodiment 1.
Its properties-correcting agent consumption is the modified effect of desulfurization slag simultaneously not, sees Table 4 and see Table 5:
The modified effect of desulfurization slag during the different properties-correcting agent consumption of table 4
| The sweetening agent prescription | 15％Mg+80％CaO+5％CaF 2 | |||
| The properties-correcting agent consumption, Kg | 0 | 40 | 60 | 80 |
| Slag-removing time, min | 10 | 7.2 | 6.8 | 8.1 |
| TFe，％ | 79 | 36 | 16 | 18 |
According to top embodiment, after adding melted iron desulfuration pretreatment furnace slag modifier, slag iron separates better, and slag iron is easy to remove, and slag-removing time reduces, and finally causes activity time and operation temperature drop all to reduce.Therefore, the desulfurization slag is taken off totally behind the adding melted iron desulfuration pretreatment furnace slag modifier, has taken off the back molten iron band quantity of slag and has reduced.
The present invention has adopted in melted iron desulfuration pretreatment furnace slag modifier and has contained Na
2The compound soda that the O amount is higher and other contain Na
2The component of O, the Na in the properties-correcting agent
2O can participate in desulphurization reaction directly, and the desulfurization of properties-correcting agent itself shows that the partition ratio of sulphur in properties-correcting agent and molten iron can reach 36-60, thereby has increased the desulfurization degree of sweetening agent and contained time sulphur phenomenon of desulfurization slag.Simultaneously, raw materials used being easy to of melted iron desulfuration pretreatment furnace slag modifier obtained, and be cheap, thereby the melted iron desulfuration pretreatment furnace slag modifier cost is low.So this properties-correcting agent has good modified effect to the desulfurization slag of CaO-Mg.
1) discover, involved in the present invention be modification to CaO-Mg desulfurization slag, when CaO content in the properties-correcting agent is controlled at less than 6% the time, have low fusing point to guarantee slag, help improving the slag rheological characteristics and assemble performance.When the CaO too high levels, the higher modification that is unfavorable for slag of the fusing point of desulfurization slag is so be controlled at CaO content about 2～6% in the present invention.
2) discover, contain SiO in the properties-correcting agent
2No matter component is to aggregate into compound or Individual existence with other oxide compounds, and the effect of remarkable gathering CaO-Mg desulfurization slag is all arranged, and helps removing of slag.But SiO
2Too high levels will make slag viscosity increase, slag iron inferior separating effect, so in the present invention, with SiO
2Content is controlled in the 49-57%.Contain K in the properties-correcting agent simultaneously
2O+Na
2The O component is improved the rheological characteristics of CaO-Mg desulfurization slag, but the too high levels etching apparatus, so in the present invention, with K
2O+Na
2O content is controlled at 15-25%.
3) this properties-correcting agent can be prepared by following starting material, glass powder, potassium felspar sand, fluorite and soda.The chemical constitution of raw material is respectively, glass powder: SiO
269～72%, CaO 10～11%, Na
2O 10～15%, 0＜Al
2O
3＜2.0%, 0＜S＜0.03%, 0＜MgO＜0.86%, 0＜Fe
2O
3＜0.9%; Potassium felspar sand: SiO
274～80%, Al
2O
310～14%, K
2O+Na
2O 8～10%; Fluorite: CaF
285～90%, 0＜SiO
2＜5.0%, 0＜S＜0.05%; Soda: Na
2CO
3＞95% (at high temperature is decomposed into Na
2O+CO
2).
Claims (6)
1. a melted iron desulfuration pretreatment furnace slag modifier is characterized in that, this properties-correcting agent is preparation of raw material by glass powder, potassium felspar sand, fluorite, soda, and the chemical component weight % of this melted iron desulfuration pretreatment furnace slag modifier is: SiO
249～57%, CaF
218～25%, Al
2O
32～5%, CaO 2～6% and K
2O+Na
2O 15～25%.
2. a kind of melted iron desulfuration pretreatment furnace slag modifier according to claim 1 is characterized in that CaO content is less than 6% in this properties-correcting agent.
3. according to the described melted iron desulfuration pretreatment furnace slag modifier of claim 1, it is characterized in that the chemical component weight % of this melted iron desulfuration pretreatment furnace slag modifier is: SiO
250%, CaF
219%, Al
2O
33%, CaO 3% and K
2O+Na
2O 24%.
4. according to the described melted iron desulfuration pretreatment furnace slag modifier of claim 1, it is characterized in that the chemical component weight % of this melted iron desulfuration pretreatment furnace slag modifier is: SiO
252%, CaF
218%, Al
2O
34%, CaO 4% and K
2O+Na
2O 21%.
5. melted iron desulfuration pretreatment furnace slag modifier according to claim 1 is characterized in that, wherein the chemical constitution of raw material satisfies respectively:
Glass powder: SiO
269～72%, CaO 10～11%, Na
2O 10～15%, 0＜Al
2O
3＜2.0%, 0＜S＜0.03%, 0＜MgO＜0.86%, 0＜Fe
2O
3＜0.9%;
Potassium felspar sand: SiO
274～80%, Al
2O
310～14%, K
2O+Na
2O 8～10%;
Fluorite: CaF
285～90%, 0＜SiO
2＜5.0%, 0＜S＜0.05%;
Soda: Na
2CO
3＞95%, Na
2CO
3At high temperature be decomposed into Na
2O+CO
2
6. the preparation method of melted iron desulfuration pretreatment furnace slag modifier according to claim 1 is characterized in that comprising following steps:
1) chemical ingredients of detection starting material glass powder, potassium felspar sand, fluorite and soda;
2) the chemical component weight % according to melted iron desulfuration pretreatment furnace slag modifier is: SiO
249～57%, CaF
218～25%, Al
2O
32～5%, CaO 2～6% and K
2O+Na
2O 15～25%, calculate required raw-material weight;
3) the above-mentioned raw materials fragmentation is worked into 200 orders;
4) in pan-type pelletizer, add broken good starting material, all mixed 5～10 minutes by prescription; Add weight % more at a slow speed and be 1.0～1.5% normal-temperature water, the granulation material is discharged in granulation 8～15 minutes;
5) send the granulation material to the drying bed inner drying, moisture content is less than 0.5%, and granularity packs stand-by at 3～5mm.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
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| CN100594242C (en) * | 2008-07-28 | 2010-03-17 | 武汉钢铁(集团)公司 | Slag diluent for molten iron desulphurization slag |
| CN102796847A (en) * | 2012-08-31 | 2012-11-28 | 宝山钢铁股份有限公司 | Premelting type molten iron slag regulator capable of reducing melting point of desulfurized molten iron slag |
| CN104032096A (en) * | 2014-06-19 | 2014-09-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Desulfurization slag modifying agent and molten iron desulfurization method |
| CN104032094A (en) * | 2014-06-19 | 2014-09-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Desulfurization slag modifying agent and molten iron desulfurization method |
| CN104294008A (en) * | 2014-10-28 | 2015-01-21 | 攀枝花钢城集团有限公司 | Hot metal desulfurization agent and application |
| CN104694688A (en) * | 2015-04-01 | 2015-06-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Magnesium compound desulfuration slag slag-state regulator and magnesium compound desulfuration slag-regulation method |
| CN110218840A (en) * | 2019-06-24 | 2019-09-10 | 鞍钢股份有限公司 | A kind of high-titanium molten iron dreg modifying agent and slag iron separation method |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100594242C (en) * | 2008-07-28 | 2010-03-17 | 武汉钢铁(集团)公司 | Slag diluent for molten iron desulphurization slag |
| CN102796847A (en) * | 2012-08-31 | 2012-11-28 | 宝山钢铁股份有限公司 | Premelting type molten iron slag regulator capable of reducing melting point of desulfurized molten iron slag |
| CN104032096A (en) * | 2014-06-19 | 2014-09-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Desulfurization slag modifying agent and molten iron desulfurization method |
| CN104032094A (en) * | 2014-06-19 | 2014-09-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Desulfurization slag modifying agent and molten iron desulfurization method |
| CN104032094B (en) * | 2014-06-19 | 2016-01-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of desulfurization slag properties-correcting agent and desulfurizing iron |
| CN104032096B (en) * | 2014-06-19 | 2016-01-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of desulfurization slag properties-correcting agent and desulfurizing iron |
| CN104294008A (en) * | 2014-10-28 | 2015-01-21 | 攀枝花钢城集团有限公司 | Hot metal desulfurization agent and application |
| CN104694688A (en) * | 2015-04-01 | 2015-06-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Magnesium compound desulfuration slag slag-state regulator and magnesium compound desulfuration slag-regulation method |
| CN104694688B (en) * | 2015-04-01 | 2017-03-15 | 攀钢集团攀枝花钢铁研究院有限公司 | The compound desulfurization slag slag state regulator of magnesium and the compound desulfurization Slag modification method of magnesium |
| CN110218840A (en) * | 2019-06-24 | 2019-09-10 | 鞍钢股份有限公司 | A kind of high-titanium molten iron dreg modifying agent and slag iron separation method |
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